JPH07218423A - Instrument for optically measuring liquid - Google Patents

Instrument for optically measuring liquid

Info

Publication number
JPH07218423A
JPH07218423A JP6012654A JP1265494A JPH07218423A JP H07218423 A JPH07218423 A JP H07218423A JP 6012654 A JP6012654 A JP 6012654A JP 1265494 A JP1265494 A JP 1265494A JP H07218423 A JPH07218423 A JP H07218423A
Authority
JP
Japan
Prior art keywords
liquid
optical fiber
suction
space
fiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP6012654A
Other languages
Japanese (ja)
Other versions
JP2706616B2 (en
Inventor
Katsu Motosawa
克 本澤
Kazuhiro Atsumi
一弘 渥美
Fumihiko Shimomura
文彦 下村
Seiji Kawaguchi
成治 川口
Yuichiro Sakamoto
裕一郎 坂本
Hisaya Motojima
久也 本島
Masayuki Masuko
正行 増子
Takeshi Hayakawa
毅 早川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BIO SENSOR KENKYUSHO KK
Original Assignee
BIO SENSOR KENKYUSHO KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BIO SENSOR KENKYUSHO KK filed Critical BIO SENSOR KENKYUSHO KK
Priority to JP6012654A priority Critical patent/JP2706616B2/en
Priority to EP95300194A priority patent/EP0666472A2/en
Priority to US08/378,369 priority patent/US5523845A/en
Publication of JPH07218423A publication Critical patent/JPH07218423A/en
Application granted granted Critical
Publication of JP2706616B2 publication Critical patent/JP2706616B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation
    • G01N21/15Preventing contamination of the components of the optical system or obstruction of the light path
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/10Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices
    • G01N2035/1027General features of the devices
    • G01N2035/1048General features of the devices using the transfer device for another function
    • G01N2035/1062General features of the devices using the transfer device for another function for testing the liquid while it is in the transfer device

Landscapes

  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Optical Measuring Cells (AREA)

Abstract

PURPOSE:To provide an optical measuring instrument for liquid which can measure a liquid to be measured with high sensitivity by directly irradiating the liquid with light from an optical fiber without contaminating the optical fiber. CONSTITUTION:The first branch fiber la of an optical fiber 1 is connected to a light source 2 and the second branch fiber 1b is connected to a photodetector 3. A tapered tip 8 is put on the front end of the fiber 11 and a tip fitting jig 4 united with the chip 8 in one body is put on the fiber 1 so that the space 7 in the tip 8 can be connected to an aspirator 11 through the gap 5 between the jig 4 and fiber 1 and a suction tube 10. Because of the aspirator 11, a liquid is drawn in the space 7 by suction through a suction port 6. The aspirator 11 is connected to a controller 12.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、光ファイバを用いて検
体液など各種液体の光吸収、光散乱、蛍光や化学発光を
簡便に測定する光学的測定装置に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical measuring device for easily measuring light absorption, light scattering, fluorescence and chemiluminescence of various liquids such as a sample liquid using an optical fiber.

【0002】[0002]

【従来の技術】光ファイバを用いて検体液の蛍光や化学
発光を測定する場合、この検体液を採取容器から測定用
に作られた光学的に透明な容器に一度移し変え、この測
定用容器内に光を照射して測定している。また、採取容
器内に収容された検体液中に直接光ファイバの端末を差
込んで測定する方法がとられることもある。
2. Description of the Related Art When measuring fluorescence or chemiluminescence of a sample liquid using an optical fiber, the sample liquid is once transferred from a sampling container to an optically transparent container made for measurement, It measures by irradiating the inside with light. In addition, a method may be adopted in which the end of the optical fiber is directly inserted into the sample liquid contained in the collection container for measurement.

【0003】[0003]

【発明が解決しようとする課題】測定用に作られた容器
を用いて液体を測定する場合は、この容器の壁の厚さ分
だけ検体液と光ファイバーは遠ざけられるため集光効率
が低下する。一方、検体液中に直接光ファイバを差し込
んで測定する場合は、光ファイバが汚染されるという問
題がある。
When a liquid is measured using a container made for measurement, the sample liquid and the optical fiber are separated by the thickness of the wall of the container, so that the light collection efficiency decreases. On the other hand, when the optical fiber is directly inserted into the sample liquid for measurement, there is a problem that the optical fiber is contaminated.

【0004】本発明は上記の問題点を解決したもので、
その目的は、光ファイバを用いて検体液を直接照射して
集光効率の高い測定を行ない、なおかつ光ファイバを汚
染することのない測定装置を提供することにある。
The present invention solves the above problems,
It is an object of the present invention to provide a measuring apparatus that directly irradiates a sample liquid with an optical fiber to perform measurement with high light collection efficiency and does not contaminate the optical fiber.

【0005】[0005]

【課題を解決するための手段】上記の目的を達成するた
め、本発明は光ファイバを用いた液体の光学的検出装置
において、光ファイバの端末に取付けられ、内部に空間
を有し、かつこの空間に通じる吸引口を有するチップ
と、当該空間に上記吸引口から被測定用の液体を吸入す
るため当該空間と連通された吸引手段を備えていること
を特徴とする。
In order to achieve the above-mentioned object, the present invention is an optical optical liquid detecting device using an optical fiber, which is attached to the end of the optical fiber and has a space inside thereof. It is characterized by comprising a chip having a suction port that communicates with the space and a suction means that is in communication with the space for sucking the liquid to be measured from the suction port into the space.

【0006】上記空間と上記吸引手段とは、上記光ファ
イバの内部または外部に形成される間隙を介して連通さ
せるとよい。この場合、光ファイバ内の間隙はバンドル
ファイバの各光ファイバ間の間隙によって形成し、ま
た、光ファイバの外部の間隙は、チップと一体の筒状チ
ップ取付け治具を光ファイバに嵌合することにより形成
するとよい。
The space and the suction means may be communicated with each other through a gap formed inside or outside the optical fiber. In this case, the gap inside the optical fiber is formed by the gap between the optical fibers of the bundle fiber, and the gap outside the optical fiber is obtained by fitting the cylindrical chip mounting jig integrated with the chip to the optical fiber. It is good to form by.

【0007】さらに、吸引手段は制御装置と接続し、こ
の制御装置の出力信号によって液体の上記空間への吸引
量または吸引速度を制御可能に設けるとよい。
Further, it is preferable that the suction means is connected to a control device, and the suction amount or the suction speed of the liquid into the space can be controlled by an output signal of the control device.

【0008】[0008]

【作用】上記の構成によると、チップの吸引口を被測定
用の液体中に少し浸漬し、吸引手段によりチップ内の空
間の空気を吸引することにより、液体は当該空間に吸引
される。このとき、空間内の液面とファイバ端面との間
隔が所定寸法になった時点で吸引手段を駆動停止する。
こうすることで、光ファイバの端面を汚染することな
く、しかも、液体を直接照射して集光効率を高くし、液
体の吸収、散乱だけでなく、蛍光や化学発光を簡便で高
感度に測定することが可能となる。
According to the above structure, the suction port of the chip is slightly dipped in the liquid to be measured, and the air in the space inside the chip is sucked by the suction means, whereby the liquid is sucked into the space. At this time, when the distance between the liquid surface in the space and the fiber end surface reaches a predetermined dimension, the driving of the suction means is stopped.
By doing this, without contaminating the end face of the optical fiber, the liquid can be directly irradiated to enhance the light collection efficiency, and not only the absorption and scattering of the liquid but also the fluorescence and chemiluminescence can be easily measured with high sensitivity. It becomes possible to do.

【0009】さらに、上記チップ内で特定物質を検出す
るための反応を進行させる場合、被測定用の液体の吸引
速度を制御することで最適な検出条件を設定することが
可能かつ容易である。
Further, when the reaction for detecting the specific substance is advanced in the chip, it is possible and easy to set the optimum detection condition by controlling the suction speed of the liquid to be measured.

【0010】[0010]

【実施例】以下本発明の実施例を図を参照して説明す
る。
Embodiments of the present invention will now be described with reference to the drawings.

【0011】光ファイバ1はY字型の3mmφ 〜7m
φ の分岐光ファイバで、第1の分岐ファイバ1aの
端部は、被測定液を励起するための略250nm〜18
00nmの光を導入するため、キセノンランプまたはハ
ロゲンランプからなる光源2に導かれている。第2の分
岐ファイバ1bの端部は、被測定液(後述する)からの
光をフォトンカウンター、フォトンマルチチャンネルア
ナライザーなどからなる光検出器3にガイドすべく当該
光検出器3に導かれている。
[0011] The optical fiber 1 of the Y-shaped 3mm φ ~7m
In the branch optical fiber m phi, the ends of the first branch fiber 1a is approximately for exciting the target solution 250nm~18
In order to introduce the light of 00 nm, it is guided to the light source 2 composed of a xenon lamp or a halogen lamp. The end of the second branch fiber 1b is guided to the photodetector 3 so as to guide the light from the liquid to be measured (described later) to the photodetector 3 including a photon counter, a photon multi-channel analyzer and the like. .

【0012】第1の分岐ファイバ1aと第2の分岐ファ
イバ1bが融合した光ファイバ1の端末には、先端がテ
ーパ部4aとされた筒状のチップ取付け治具4が、光フ
ァイバ1との間に間隙5を有して嵌合され、かつ固定さ
れている。
At the end of the optical fiber 1 in which the first branch fiber 1a and the second branch fiber 1b are fused, a cylindrical chip mounting jig 4 having a tapered portion 4a at the end is connected to the optical fiber 1. They are fitted and fixed with a gap 5 therebetween.

【0013】チップ取付け治具4の先端には、吸引口6
を有するとともに、内部に空間7を有するテーパ型チッ
プ8を当てがい、それぞれのテーパ部4a,8aを接着
することで両部材が固定されている。チップ取付け治具
4からは、吸引端部10aがその周壁を貫いて上記の間
隙5に連通している吸引チューブ10が導出されてお
り、この吸引チューブ10の他端に吸引装置11が接続
されている。光検出器3及び、吸引装置11の駆動部は
それぞれ制御装置12と電気的に接続されている。
A suction port 6 is provided at the tip of the chip mounting jig 4.
Both members are fixed by applying a tapered tip 8 having a space 7 therein and bonding the respective tapered portions 4a and 8a. A suction tube 10 having a suction end portion 10a penetrating its peripheral wall and communicating with the above-mentioned gap 5 is led out from the tip mounting jig 4, and a suction device 11 is connected to the other end of this suction tube 10. ing. The photodetector 3 and the driving unit of the suction device 11 are electrically connected to the control device 12, respectively.

【0014】本実施例の装置を用いて検体液を測定する
には、まずテーパ型チップ8の吸引口6が採取容器に収
容された検体液(図示せず)の液面とほぼ接する程度
に、テーパ型チップ8の先端を当該検体液中に少し浸漬
する。
In order to measure the sample liquid using the apparatus of this embodiment, first, the suction port 6 of the tapered tip 8 is brought into contact with the liquid surface of the sample liquid (not shown) contained in the sampling container. The tip of the tapered tip 8 is slightly dipped in the sample liquid.

【0015】つづいて、吸引装置11を駆動し、間隙5
と吸引チューブ10を介してテーパ型チップ8内の空間
7の空気を吸引すると、空間7が負圧となり吸引口6か
らこの空間7に測定に必要な量の検体液13が分取され
る。この場合、テーパ型チップ8内の検体液13の液面
14が、ファイバ端面15と極めて接近できる(間隔L
は約3.0mm以下)ように当該検体液13の吸引量と
吸引速度とが設定されている。具体的に説明すると、本
実施例では、検体液13の吸引量は100μL〜1m
L、吸引速度は0.1mL/secに設定されている。
Subsequently, the suction device 11 is driven to move the gap 5
When the air in the space 7 in the tapered tip 8 is sucked through the suction tube 10, the space 7 becomes a negative pressure and the amount of the sample liquid 13 required for measurement is dispensed from the suction port 6 into the space 7. In this case, the liquid surface 14 of the sample liquid 13 in the tapered tip 8 can be extremely close to the fiber end surface 15 (interval L
Is about 3.0 mm or less), the suction amount and the suction speed of the sample liquid 13 are set. More specifically, in the present embodiment, the suction amount of the sample liquid 13 is 100 μL to 1 m.
L, the suction speed is set to 0.1 mL / sec.

【0016】なお、吸引量の設定については、例えばテ
ーパ型チップ8内に液面センサ(図示せず)を設け、こ
の液面センサの信号を制御装置12で処理し、制御装置
12からの信号で吸引装置11の駆動源の駆動を微調整
することで行なうことができる。
For setting the suction amount, for example, a liquid level sensor (not shown) is provided in the tapered tip 8, the signal of this liquid level sensor is processed by the controller 12, and the signal from the controller 12 is set. Can be performed by finely adjusting the drive of the drive source of the suction device 11.

【0017】その後、光源2からの励起光を、第1の分
岐ファイバ1aと光ファイバ1を通してファイバ端面1
5から被測定用の検体液13に照射し、この光照射に伴
なう検体液13からの蛍光を光ファイバ1と第2の分岐
ファイバ1bを通して光検出器3に導く。この光検出器
3の内部では、励起光を除去するため、干渉フィルター
や分光装置による波長選択が行なわれ、目的物質である
検体液13の蛍光のみが測定される。
After that, the excitation light from the light source 2 passes through the first branch fiber 1a and the optical fiber 1 and the fiber end face 1
The sample liquid 13 to be measured is irradiated from 5 and the fluorescence from the sample liquid 13 accompanying this light irradiation is guided to the photodetector 3 through the optical fiber 1 and the second branch fiber 1b. Inside the photodetector 3, wavelengths are selected by an interference filter or a spectroscopic device in order to remove the excitation light, and only the fluorescence of the sample liquid 13 which is the target substance is measured.

【0018】なお、上記の測定で、光検出器3内部での
波長選択を励起光波長に合わせることで、被測定液の濁
度測定も可能になる。
In the above measurement, the turbidity of the liquid to be measured can be measured by adjusting the wavelength selection inside the photodetector 3 to the wavelength of the excitation light.

【0019】上記一連の操作つまり、検体液の吸引、励
起光の照射、蛍光の測定等は制御装置12の設定に従っ
て自動で行なわれ、測定結果の表示、記録も同時に行な
われる。
The above series of operations, that is, the suction of the sample liquid, the irradiation of the excitation light, the measurement of the fluorescence and the like are automatically performed according to the setting of the control device 12, and the measurement results are displayed and recorded at the same time.

【0020】上記の測定に際し、検体液13の液面14
がファイバ端面15に極めて接近した位置に設定できる
ので、検体液13からの蛍光は再現性よく高感度に検出
される。
During the above measurement, the liquid surface 14 of the sample liquid 13
Can be set at a position extremely close to the fiber end face 15, so that fluorescence from the sample liquid 13 can be detected with high reproducibility and high sensitivity.

【0021】なお、本実施例では、テーパ型チップ8内
の空間7を吸引するための間隙5は、光ファイバ1の外
周部と筒状のチップ取付け治具4との間に形成されてい
るが、間隙の形成手段はこれに限定されない。例えば多
数の光ファイバを束ねて形成されるバンドルファイバ
(図示せず)内の間隙を利用して上記テーパ型チップ8
内の空間7を吸引するようにしてもよい。その他、吸引
チューブを空間7に直接導く(図示せず)ことも可能で
あり、その場合は上記の間隙5も不要である。
In this embodiment, the gap 5 for sucking the space 7 in the tapered tip 8 is formed between the outer peripheral portion of the optical fiber 1 and the cylindrical tip mounting jig 4. However, the means for forming the gap is not limited to this. For example, the taper type chip 8 is utilized by utilizing a gap in a bundle fiber (not shown) formed by bundling a large number of optical fibers.
The internal space 7 may be sucked. Besides, it is also possible to directly guide the suction tube to the space 7 (not shown), and in that case, the above-mentioned gap 5 is also unnecessary.

【0022】[0022]

【発明の効果】以上説明したように、本発明に係る液体
の光学的測定装置によれば、光ファイバの端面から被測
定液の液面に直接励起光を照射して集光効率を高くし、
液面の蛍光や化学発光を高感度に検出でき、しかもファ
イバ端面が液体と僅か離れているので光ファイバが汚染
されることがない。また、ファイバ端面と液面との間の
微小な間隙設定が、ファイバ端面に取付けたチップ内の
空間を吸引するという手段により簡易に実現できる。さ
らに、被測定液内の特定な物質を検出するため反応を進
行させる場合は、この被測定液の吸引速度を制御するこ
とで最適な検出条件を設定することが容易である。
As described above, according to the optical liquid measuring device of the present invention, the excitation light is directly irradiated from the end face of the optical fiber to the liquid surface of the liquid to be measured to enhance the light collecting efficiency. ,
Fluorescence and chemiluminescence on the liquid surface can be detected with high sensitivity, and since the fiber end surface is slightly separated from the liquid, the optical fiber is not contaminated. Further, setting of a minute gap between the fiber end surface and the liquid surface can be easily realized by means of sucking the space in the chip attached to the fiber end surface. Furthermore, when the reaction is allowed to proceed to detect a specific substance in the liquid to be measured, it is easy to set the optimum detection condition by controlling the suction speed of the liquid to be measured.

【図面の簡単な説明】[Brief description of drawings]

【図1】実施例に係る液体の光学的測定装置の説明図で
ある。
FIG. 1 is an explanatory diagram of an optical liquid measuring device according to an embodiment.

【図2】図1のA部の拡大断面図である。FIG. 2 is an enlarged cross-sectional view of a portion A of FIG.

【符号の説明】[Explanation of symbols]

1…光ファイバ、2…光源、3…光検出器、4…チップ
取付け治具、5…間隙、6…吸引口、7…空間、8…テ
ーパ型チップ、11…吸引装置、12…制御装置、13
…液体。
1 ... Optical fiber, 2 ... Light source, 3 ... Photodetector, 4 ... Chip mounting jig, 5 ... Gap, 6 ... Suction port, 7 ... Space, 8 ... Tapered chip, 11 ... Suction device, 12 ... Control device , 13
…liquid.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 川口 成治 神奈川県綾瀬市早川2743−1 東ソー株式 会社内 (72)発明者 坂本 裕一郎 東京都豊島区高田3−41−8 中外製薬株 式会社内 (72)発明者 本島 久也 東京都豊島区高田3−41−8 中外製薬株 式会社内 (72)発明者 増子 正行 静岡県浜松市市野町1126番地の1 浜松ホ トニクス株式会社内 (72)発明者 早川 毅 静岡県浜松市市野町1126番地の1 浜松ホ トニクス株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naruharu Kawaguchi 2743-1, Hayakawa, Ayase-shi, Kanagawa Tosoh Corporation (72) Inventor Yuichiro Sakamoto 3-41-8 Takada, Toshima-ku, Tokyo Chugai Pharmaceutical Co., Ltd. (72) Inventor Hisaya Motoshima 3-41-8 Takada, Toshima-ku, Tokyo Chugai Pharmaceutical Co., Ltd. (72) Inventor Masayuki Masuko 1 126-1, Nomachi, Hamamatsu, Shizuoka Prefecture Hamamatsu Photonics KK (72) Invention Takeshi Hayakawa 1 Hamamatsu Photonics Co., Ltd. 1 No. 1126 Nomachi, Hamamatsu City, Shizuoka Prefecture

Claims (5)

【特許請求の範囲】[Claims] 【請求項1】 光ファイバを用いた液体の光学的検出装
置において、光ファイバの端末に取付けられ、内部に空
間を有し、かつこの空間に通じる吸引口を有するチップ
と、前記空間に前記吸引口から被測定用の液体を吸入す
るため当該空間と連通された吸引手段を備えてなる液体
の光学的測定装置。
1. A liquid optical detection device using an optical fiber, wherein the tip is attached to the end of the optical fiber, has a space inside, and has a suction port communicating with this space, and the suction in the space. An optical measuring device for a liquid, comprising suction means communicating with the space for sucking the liquid to be measured from the mouth.
【請求項2】 前記空間は、前記光ファイバの内部又は
外部に形成される間隙を介して前記吸引手段と連通され
てなる請求項1記載の液体の光学的測定装置。
2. The optical measuring apparatus for liquid according to claim 1, wherein the space is communicated with the suction means through a gap formed inside or outside the optical fiber.
【請求項3】 前記光ファイバの外部に形成される間隙
は、前記チップと一体の筒状のチップ取付け治具を前記
光ファイバに嵌合することにより形成される間隙である
請求項1記載の液体の光学的測定装置。
3. The gap formed outside the optical fiber is a gap formed by fitting a cylindrical chip mounting jig integral with the chip to the optical fiber. Liquid optical measuring device.
【請求項4】 前記光ファイバの内部に形成される間隙
は、バンドルファイバの各光ファイバ間に形成される間
隙である請求項1記載の液体の光学的測定装置。
4. The optical liquid measuring device according to claim 1, wherein the gap formed inside the optical fiber is a gap formed between the optical fibers of the bundle fiber.
【請求項5】 前記吸引手段は、前記液体の前記空間へ
の吸引量または吸引速度を制御可能な制御装置に接続さ
れている請求項1ないし4のいずれかに記載の液体の光
学的測定装置。
5. The liquid optical measuring apparatus according to claim 1, wherein the suction means is connected to a control device capable of controlling a suction amount or a suction speed of the liquid into the space. .
JP6012654A 1994-02-04 1994-02-04 Liquid optical measuring device Expired - Fee Related JP2706616B2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP6012654A JP2706616B2 (en) 1994-02-04 1994-02-04 Liquid optical measuring device
EP95300194A EP0666472A2 (en) 1994-02-04 1995-01-12 Device for optically measuring liquids
US08/378,369 US5523845A (en) 1994-02-04 1995-01-25 A fiber optic device for measuring liquids which are drawn into an end of the device to a predetermined distance from the end of the optical fibers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6012654A JP2706616B2 (en) 1994-02-04 1994-02-04 Liquid optical measuring device

Publications (2)

Publication Number Publication Date
JPH07218423A true JPH07218423A (en) 1995-08-18
JP2706616B2 JP2706616B2 (en) 1998-01-28

Family

ID=11811356

Family Applications (1)

Application Number Title Priority Date Filing Date
JP6012654A Expired - Fee Related JP2706616B2 (en) 1994-02-04 1994-02-04 Liquid optical measuring device

Country Status (3)

Country Link
US (1) US5523845A (en)
EP (1) EP0666472A2 (en)
JP (1) JP2706616B2 (en)

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Also Published As

Publication number Publication date
EP0666472A3 (en) 1995-09-06
US5523845A (en) 1996-06-04
EP0666472A2 (en) 1995-08-09
JP2706616B2 (en) 1998-01-28

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